Shallow and Deep States of Beryllium Acceptor in GaN: Why Photoluminescence Experiments Do Not Reveal Small Polarons for Defects in Semiconductors.

Currently, only one shallow acceptor (Mg) has been discovered in GaN. Here, using photoluminescence (PL) measurements combined with hybrid density functional theory, we demonstrate that a shallow effective-mass state also exists for the Be_{Ga} acceptor. A PL band with a maximum at 3.38 eV reveals a shallow Be_{Ga} acceptor level at 113±5 meV above the valence band, which is the lowest value among any dopants in GaN reported to date. Calculations suggest that the Be_{Ga} is a dual-nature acceptor with the "bright" shallow state responsible for the 3.38 eV PL band, and the "dark," strongly localized small polaronic state with a significantly lower hole capture efficiency.

Determination of the concentration of impurities in GaN from photoluminescence and secondary-ion mass spectrometry.

Photoluminescence (PL) was used to estimate the concentration of carbon in GaN grown by hydride vapor phase epitaxy (HVPE). The PL data were compared with profiles of the impurities obtained from secondary ion mass spectrometry (SIMS) measurements. Comparison of PL and SIMS data has revealed that apparently high concentrations of C and O at depths up to 1 µm in SIMS profiles do not represent depth distributions of these species in the GaN matrix but are rather caused by post-growth surface contamination and knocking-in impurity species from the surface. In particular, PL analysis supplemented by reactive ion etching up to the depth of 400 nm indicates that the concentration of carbon in nitrogen sites is below 2-5 × 1015 cm-3 at any depth of GaN samples grown by HVPE. We demonstrate that PL is a very sensitive and reliable tool to determine the concentrations of impurities in the GaN matrix.

Two yellow luminescence bands in undoped GaN.

Two yellow luminescence bands related to different defects have been revealed in undoped GaN grown by hydride vapor phase epitaxy (HVPE). One of them, labeled YL1, has the zero-phonon line (ZPL) at 2.57 eV and the band maximum at 2.20 eV at low temperature. This luminescence band is the ubiquitous yellow band observed in GaN grown by metalorganic chemical vapor deposition, either undoped (but containing carbon with high concentration) or doped with Si. Another yellow band, labeled YL3, has the ZPL at 2.36 eV and the band maximum at 2.09 eV. Previously, the ZPL and fine structure of this band were erroneously attributed to the red luminescence band. Both the YL1 and YL3 bands show phonon-related fine structure at the high-energy side, which is caused by strong electron-phonon coupling involving the LO and pseudo-local phonon modes. The shapes of the bands are described with a one-dimensional configuration coordinate model, and the Huang-Rhys factors are found. Possible origins of the defect-related luminescence bands are discussed.

Evaluation of the concentration of point defects in GaN.

Photoluminescence (PL) was used to estimate the concentration of point defects in GaN. The results are compared with data from positron annihilation spectroscopy (PAS), secondary ion mass spectrometry (SIMS), and deep level transient spectroscopy (DLTS). Defect-related PL intensity in undoped GaN grown by hydride vapor phase epitaxy increases linearly with the concentration of related defects only up to 1016 cm-3. At higher concentrations, the PL intensity associated with individual defects tends to saturate, and accordingly, does not directly correlate with the concentration of defects. For this reason, SIMS analysis, with relatively high detection limits, may not be helpful for classifying unidentified point defects in GaN. Additionally, we highlight challenges in correlating defects identified by PL with those by PAS and DLTS methods.

Determination of the electron-capture coefficients and the concentration of free electrons in GaN from time-resolved photoluminescence.

Point defects in high-purity GaN layers grown by hydride vapor phase epitaxy are studied by steady-state and time-resolved photoluminescence (PL). The electron-capture coefficients for defects responsible for the dominant defect-related PL bands in this material are found. The capture coefficients for all the defects, except for the green luminescence (GL1) band, are independent of temperature. The electron-capture coefficient for the GL1 band significantly changes with temperature because the GL1 band is caused by an internal transition in the related defect, involving an excited state acting as a giant trap for electrons. By using the determined electron-capture coefficients, the concentration of free electrons can be found at different temperatures by a contactless method. A new classification system is suggested for defect-related PL bands in undoped GaN.

Yellow luminescence of gallium nitride generated by carbon defect complexes.

We demonstrate that yellow luminescence often observed in both carbon-doped and pristine GaN is the result of electronic transitions via the C(N)-O(N) complex. In contrast to common isolated defects, the C(N)-O(N) complex is energetically favorable, and its calculated optical properties, such as absorption and emission energies, a zero phonon line, and the thermodynamic transition level, all show excellent agreement with measured luminescence data. Thus, by combining hybrid density functional theory and experimental measurements, we propose a solution to a long-standing problem of the GaN yellow luminescence.